Methods and materials for replenishment of developers for color photographic films (b)

ABSTRACT

Developer replenishers having buffer controlled high pH and high potassium/sodium weight ratio are effective at low-replenishment rates; for example, developer replenishers having a pH of 10.5 to 11 containing a potassium/sodium weight ratio of at least 5.4/1,p-phenylenediamine developing agent and benzyl alcohol in weight ratio of between about 1/1.5 and 1/2 and sulfite are especially effective. Such replenishers are advantageously prepared from kits comprising at least two solutions, one a buffered aqueous alkaline solution containing alkali metal ions in a high potassium/sodium weight ratio and another an aqueous solution having low pH and containing p-phenylenediamine developing agent in high concentration. The replenishers are utilized in conjunction with the processing of imagewise exposed, multilayer, incorporated coupler, silver halide sensitized, color photographic film materials.

United States Patent I Surash et al.

[ 5] Mar. 7, 1972 [72] Inventors: John J. Surash; Edward J. Giorgianni;

Lynn R. Hotter, all of Rochester, NY.

[73] Assignee: Eastman Kodak Company, Rochester,

[22] Filed: Feb. 19, 1969 211 App]. No.: 800,728

[S2] ,U.S. Cl ..96/66, 96/661 [51] Int. Cl ..G03c 5/30 [58] Field ofSearch ..96/66, 66.1, 66.4, 56.2

[56] References Cited UNITED STATES PATENTS 3,276,874 10/ 1966 Levensonet al ..96/66 3,178,284 4/1965 Oakley et al ..96/66.1 2,695,234 11/1954Jaeken et a1 ..96/562 3,490,906 1/1970 Blake ....96/66 3,459,549 8/1969McBride et al. ....96/66 3,305,364 2/1967 Bard et al. ..96/66.4

2,162,765 6/1939 Tarnoff ..96/66.1 2,552,241 5/1951 Weissberger etal.... .....260/556 2,566,271 8/1951 Weissberger et al ..96/56.6

Primary Examiner-Norman G. Torchin Assistant ExaminerEdward C. KimlinAttorney-Walter O. l-lodsdon and Dwight J. Holte [57] ABSTRACT Developerreplenishers having buffer controlled high pH and high potassium/sodiumweight ratio are efiective at lowreplenishment rates;-for example,developer replenishers having a pH of 10.5 to 11 containing apotassium/sodium weight ratio of at least 5.4/l,p-phenylenediaminedeveloping agent and benzyl alcohol in weight ratio of between about l/l .5 and U2 and sulfite are especially effective. Such replenishers areadvantageously prepared from kits comprising at least two solutions, onea buffered aqueous alkaline solution containing alkali metal ions in ahigh potassium/sodium weight ratio and another an aqueous solutionhaving low pH and containing pphenylenediamine developing agent in highconcentration. The replenishers are utilized in conjunction with theprocessing of imagewise exposed, multilayer, incorporated coupler,silver halide sensitized, color photographic film materials.

18 Claims, No Drawings METHODS AND MATERIALS FOR REPLENISHMENT OFDEVELOPERS FOR COLOR PHOTOGRAPHIC FILMS (B) This invention relates todeveloper replenishers which can be effectively utilized in thecontinuous processing of imagewise exposed, silver halide sensitized,color photographic film materials. in one of its aspects this inventionrelates to methods and materials effectively used in preparing suchdeveloper replenishers. In another of its aspects this invention relatesto continuous processes in which such developer replenishers areemployed.

The processing of imagewise exposed, multilayer, incorporated coupler,silver halide sensitized, color photographic film materials of thepositive-negative type (that is, those which on exposure to a subject orpositive image and processing are designed to result in a negative colorimage which can be used as a negative from which photographic colorprints are made, or conversely on exposure to a negative are designed toform a positive transparency) usually involves subjecting the film to aseries of processing steps by, for example, passing the film through anumber of different processing compositions. These steps include:developing the film in an aqueous alkaline solution which containsp-phenylenediamine developing agent to simultaneously form silver imagesand dye images in the exposed areas; stopping the development bytreating the film with an acidic composition; hardening the developedfilm by treating the film with a gelatin-hardening composition;bleaching the hardened film by treating the film with a bleachcomposition to convert developed silver to AG; and fixing AG includingunexposed silver halide, from the bleached film by treating the filmwith a fixing composition.

Several of the compositions used in this type of process loseeffectiveness in their intended function after use for a period of time.The developer loses its effectiveness, for example, because some of thedeveloper components react with components of the film Thep-phenylenediamine developing agent, for example, reacts withincorporated color couplers of the film to form dyes in areas which havereceived exposure. Also, some of the developer is lost as carryover whenfilm is passed through a bath or series of baths of developer. As aresult of the loss in effectiveness of the developer, the compositionmust be replaced or treated to restore its effectiveness.

In a continuous process, i.e., one designed for operation for largequantities of film over an extended period of time, the effectiveness ofsuch.- compositions is restored by adding developer replenisher to theoriginal solution. The concentration of the developer replenishercomponents are thus controlled to maintain desirable developer componentconcentrations between predetermined limits, usually at a relativelyconstant value. The replenisher must not only make up for componentsused during processing and loss through carryover, but also overflowloss by volume increase when the replenisher is added. The replenishmentcan be accomplished while the developer is in use by addingreplenishment in continuous fashion or at periodic intervals, usually ata specified amount of replenisher for each square foot of filmprocessed.

In such processes it has heretofore been considered necessary to use adeveloper replenishment rate of at least about 325 ml. of developerreplenisher per square foot of processed film (normally about 485 ml.per square foot of picture area) to assure high-quality, reproducibledevelopment.

We have found that by using developer replenishers having a buffercontrolled high pH and high potassium/sodium weight ratio in processingmultilayer, incorporated coupler, silver halide sensitized, colorphotographic film materials of the positive-negative type, high-qualitydevelopment can be obtained at a replenishment rate which is a fraction(one-half and even less) of the rate previously considered necessary forsatisfactory results. These surprisingly effective developerreplenishers are advantageously prepared from replenisher kits having atleast two solutions, one containing concentrated acidic developing agentsolution and another containing a concentrated aqueous solution having abuffer controlled high pH with alkali metal ions in highpotassium/sodium ratio.

According to the present invention there are provided developerreplenisher kits and components thereof which are advantageously usedfor the production of developer replenishers which can be effectivelyutilized at a surprisingly low replenishment rate.

Also, in accordance with the present invention there are providedmethods of making such developer replenishers.

Further, in accordance with the present invention there are providedimproved developer replenishers.

Additionally, according to the present invention, there are providedmethods and materials for use in conjunction with processing ofmultilayer, incorporated coupler, silver halide sensitized, color filmmaterials which result in substantial decrease in the cost of chemicalsused in developers and cost of pollution prevention with no detrimentaleffect on the overall quality of the process.

Also provided in accordance with the present invention are improvedmethods and materials for processing imagewise exposed, well-knownincorporated coupler, silver halide sensitized, color photographic filmmaterials of the positive-negative type and for utilizing replenishercompositions whereby the concentrations of desirable components inprocessing solutions are controlled between predetermined concentrationlimits.

Further advantages which result from the present invention will becomeapparent from the following description.

in one embodiment of the present invention a concentrated, bufferedaqueous solution having a pH in excess of about l0.5, advantageouslyabove about 10.75 when measured at about 75 F. (normally bufferedsolutions having a high pH decrease in pH with increase in temperature)and containing water; hydroxide; buffer, e.g., phosphate, carbonates,advantageously boric acid-borate buffer; and alkali metal ions selectedfrom the group consisting of sodium and potassium ions so that thepotassium/sodium weight ratio is at least 2.5/1, especially at least5.4/1.0, forms one component of a developer replenisher kit. Thissolution also desirably contains some sulfite (e.g., supplied as sodiumor potassium sulfite or bisulfite) and/or sequestering agent, such asethylenediamine tetraacetic acid and advantageously diaminopropanoltetraacetic acid. In some instances it is also desirable to have smallamounts of bromide present in the buffered solution.

The buffered solution can be prepared in a number of ways but it isespecially advantageous to add alkali metal hydroxides to water and thenthe weak acid to the alkaline solution to form the buffer. Thealkalimetal hydroxide/weak acid ratio used to form the buffer may vary to somedegree but it is desirably about a 1/ 1 mole ratio and advantageouslyl-l.l/l to maintain the desired pH and buffer capacity. It is especiallyadvantageous to use potassium hydroxide as the main source of hydroxidebut some sodium hydroxide can be used with effectiveness.

The potassium/sodium weight ratio for the total solution to be used asthe component for the developer replenisher kit should be at least about2.5/1, advantageously at least about 5.4/1 and especially between5.4-10/1. Thus, if alkali metal ions are introduced into the kitcomponent as cations of the other salts, e.g., as sodium sulfite, theweight ratios of hydroxides may vary. In a preferred embodiment of theinvention no cations other than sodium and potassium are present in thebuffered solution in significant concentration.

The concentration of the ingredients in the buffered solution can varyconsiderably. However, the solutions are desirably concentrated so thatshipping, packaging, and handling costs are reasonably low. However, theconcentration should be sufficiently low so that no crystallizationoccurs since such crystals are often difficult to redissolve. Solutionshaving a cationic concentration of about 7-15 molar are generallydesirable especially when the cations consist essentially of potassiumand sodium in a potassium/sodium weight ratio of at least about 2.5/ ladvantageously 5.4/1.0 and especially 5.4 to l0/l.0.

The hydroxide and weak acid concentrations desirable in such a solutionwill be dictated by the pH and buffer capacity desired but usually thealkali metal hydroxides constitute the main source of alkali metal.Accordingly, sufficient hydroxide is desirably used so that thehydroxide concentration also corresponds to about 7-15 molarconcentration were it not for the formation of the buffer. The weak acidconcentration originally used will also vary depending upon theparticular pH and buffer capacity desired. However, for formation of theboric acid-borate buffer it is advantageous to utilize thehydroxide/boric acid ratio indicated above.

The sulfite concentration of such a kit component is dictated by theamount of sulfite necessary in the replenisher. A concentration of about0.15 to about 0.4 molar in the kit component is usually desirable.Although, as mentioned above, it is sometimes desirable to have somebromide present in the kit component, it is important that the bromidecontent of the fresh, ready-to-use replenisher be no higher than about0.010 molar and advantageously no higher than 0.009 molar. Thus, if thebromide were added, for example, as sodium bromide, the total sodiumbromide used would be no greater than about 1.0 g. for sufficientconcentrate to make one liter of replenisher or no greater than about0.2 molar in the replenisher kit.

The buffered solution is advantageously one solution of a developerreplenisher kit which includes at least another solution comprisingp-phenylenediamine developing agent at high concentration in aqueoussolution having a pH less than about 6, advantageously less than about4. The p-phenylenediamine developing agents which are used in thissolution are the color developing agents well known in the art, forexample, US. Pat. Nos. 2,552,241 and 2,566,271, which form nondiffusingdyes with phenolic and reactive methylene couplers. These developingagents include N substituted or ring substituted pphenylenediamines,such as N,N-dialkyl-p-phenylenediamines wherein the alkyl groups and/orthe aromatic nucleus may be substituted, for example, with a sulfonamidogroup. Examples of highly useful developing agents are 2-amino-5-diethylaminotoluene monohydrochloride; 4-amino-N-ethyl-N-[B-methanesulfonamidoethyll-m-toluidine sesquisulfate monohydrate;4-amino-3-methyl-N-ethy1-N-[B-hydroxyethyl]-aniline sulfate; and4-amino-3-methyl-sulfonamidoethyl]fl-methyl-sulfoamidoethyl]-N,Ndiethylaniline. In an extremely advantageous embodiment of the presentinvention 4-amino-N-ethyl-N-[B-methanesulfonamidoethyl]-m-toluidinesesquisulfate monohydrate is used as the color developing agent. v

The concentration of the developing agent will, of course,

' vary depending upon the specific developing agent selected,

etc. Again, for economic reasons, it is advantageous to have a highlyconcentrated solution, particularly between about 1-6 g. diamine per 10grams of water, for the replenisher kit component. Whenfonamidoethyl]-m-toluidine is used as the developing agent it isdesirable to use a concentration of about 5 g. diamine (i.e., about 7.8g. 4-amino-N-ethyl-N-[B-methanesulfonamidoethyl]-m-toluidinesesquisulfate monohydrate) for each g. water.

The developer replenisher kit according to the present invention alsocontains sulfite. As mentioned above, sulfite is advantageously includedin the buffered solution. 1t is also desirable to include sulfite in thedeveloping agent solution desirably in a diamine/sulfite mole ratio ofabout 'l/0.08 to about 1/1.5, especially about H015 to about 1/0.5.(Mole ratios of diamine set forth herein relate to the moles ofavailable diamine in the solution not necessarily moles of salt added,e.g., 846 g. of 4-amino-N-ethyl-N-[B-methanesulfonamidoethyl]-mtoluidinesesquisulfate monohydrate, is considered to include 2 moles of diamine.)

Benzyl alcohol is also included in the developer replenisher kitaccording to the present invention and it, too, is advantageouslyincluded in the developing agent solution desirably at aphenylenediamine/benzyl alcohol weight ratio of no less than about 1/2and especially between about 1/ 1.5 and 1/2. A highly advantageousmethod of incorporating the 4-arnino-N-ethyl- N-[ B-methanesulbenzylalcohol in the concentrated developing agent solution is by utilizing asimple liquid glycol with a carbon/oxygen ratio of about 0.75 to about1.5/1 and molecular weight of from about 62 to about 150, desirably in abenzyl alcohol/glycol weight ratio between about 0.7/1 and about 1/1.Particularly advantageous glycols are propylene glycol, diethyleneglycol, and triethylene glycol, and especially ethylene glycol. Withsuch compounds the benzyl alcohol can be combined with acidic aqueoussolutions to form clear solutions in a high benzyl alcoholconcentration, a water/benzyl alcohol weight ratio of from l/6 to about5/1.

The developing agent solutions which contain benzyl alcohol may beprepared by simply combining the various ingredients. However, to obtainmaximum concentration and convenience and minimize the necessity forrechecking the component quantity accuracy, the solution is formed byfirst combining water with the desired amount of sulfite, and thendissolving the p-phenylenediamine developing agent (usually as the acidsalt) in the sulfite solution. The benzyl alcohol is then advantageouslyadded to form a cloudy slurry after which at least sufficient glycol isadded to convert the slurry into a clear solution, i.e., apparently aone phase composition.

The developer replenisher kit effectively may be a single package; forexample, an outside container in which the concentrated solutions arecompartmentalized. The compartments can be an integral part of theexterior packaging material but advantageously are, for example, glassor plastic bottles enclosed in the outside container, e.g., a cardboardbox. The choices of sizes and shapes of the bottles, etc., which formthe compartments, can vary with the selected ingredients, concentrationsdesired, etc. Usually it is desirable to choose the the bottle size,shape, etc., which will result in a total package of minimum size andweight to minimize shipping and storage costs. As a result, it may insome instances be desirable to place a single component type in aplurality of compartments,

1 e.g., to conserve space.

The developer replenisher kit ingredients should be separated duringstorage, shipping, etc., to the extent that the developing agentsolution is in a separate compartment from the buffered solution anddesirably so that the benzyl alcohol and some sulfite are in thedeveloping agent solution as mentioned above. Other components which mayfonn part of the developer replenisher kit, for example, additionalsulfite; accelerators; and complexing agents, e.g., polyphosphates,sodium hexametaphosphates, nitrilo acetic acid, methylamino diaceticacid, dimethylethylene diamino diacetic acid, ethylenediaminetetraacetic acid, and diaminopropanol tetraacetic acid, areadvantageously contained in the compartment containing the bufferedsolution, although placing the addenda in other or separate compartmentsmay be desirable depending upon the particular ingredient chosen, etc.

The developer replenisher kit is then converted into a developerreplenisher by combining the developing agent solution and the bufferedsolution with water, desirably by first mixing a concentrated developingagent solution which contains benzyl alcohol with a desired amount ofwater and subsequently adding the buffered solution and adjusting tofinal concentration by adding water.

The ready-to-use developer replenisher according to the presentinvention has a pH of about 10.5 to l 1, desirably 10.6 to about 19.9,when measured at F., and contains alkali metal cations,p-phenylenediamine developing agent, benzyl alcohol, and sulfite. Thealkali metal ions utilized are generally potassium and sodium. Althoughit is often desirable to include some sodium ions in the replenisher,the alkali metal ions must be selected so that the potassium/sodiumweight ratio is in excess of about 2.5/1, advantageously in excess ofabout 4/1, and especially above about 5.4/1. It is frequentlyadvantageous to utilize a potassium/sodium weight ratio between about4/1 and about 10/1 with ratios between 5.4/1 and 10/1 being especiallyefficacious.

The developing agents and concentrations used in the replenisher kitdesirably result in a replenisher concentration of about 3 g. to about 5g. per liter based on the weight of available diamine. (Thus, althoughabout 6 g. of Z-amino-S- diethylaminotoluene monohydrochloride may beused, there would be less than 5 g. of available diamine.) In anespecially desirable embodiment of the present invention about 3.8 to4.5 g. of 4-amino-N-ethyl-N-[B-methanesulfonamidoethyl]- m-toluidine areutilized per liter of replenisher solution.

For highly effective replenishers according to the present invention, itis important that the benzyl alcohol in the readyto-use replenisher beused at a concentration of no more than about 8 g. per liter, normallybetween about 4 to about 8 g. per liter, desirably about 6 to about 7.5g. per liter. Similarly, if any bromide is utilized in the developerreplenisher, it is important that no more than about 0.80 g. bromide beused per liter of replenisher. Thus, if the bromide is supplied to thesolution as sodium bromide, no more than about 1.0 g. should be utilizedper liter of replenisher.

The replenisher also contains sulfite desirably in concentration ofabout 1.25 g. to about 1.55 g. per liter of solution or a totalp-phenylenediamine/sulfite mole ratio of about U 1.6. As with thebromide, the sulfite is desirably supplied to the solution as an alkalimetal sulfite or bisulfite, desirably as sodium sulfite.

The replenisher also advantageously includes a buffer system asmentioned above. An especially effective buffer system is the boricacid-borate system, desirably supplied to the kit solution byincorporating therein the alkali metal hydroxides selected from thegroup consisting of potassium and sodium hydroxides so that thepotassium/sodium ratio for the replenisher is at least 2.5/1, and 18 tog. especially 25 to 30 g. boric acid per liter of replenisher solutionto maintain the pH of the solution at the desired level. The resultantreplenisher solution contains from about 19 to about 28.5 g. per literborate in various states of dissociation, i.e., boric acid and/or thedissolved borate-containing residues from the boric acid.

The other addenda indicated as being advantageously included in thedeveloper replenisher kit can also be included in the replenishersaccording to the present invention. For example, a highly effectiveembodiment of the present invention the dissolved residues fromdiaminopropanol tetraacetic acid are also included in the replenisherespecially at a concentration of about 1 to about 1.5 g. per liter ofsolution.

According to another highly advantageous embodiment of the presentinvention the developer replenishers mentioned are used in a method forprocessing imagewise exposed silver halide photographic film materialsof the positive-negative type having adhered to and superposed on atransparent support at least a red-sensitized emulsion layer containingnondiffusing cyan dye-forming coupler, a green-sensitized emulsion layercontaining nonditfusion magenta dye-forming coupler, and ablue-sensitized emulsion layer containing nondiffusing yellowdye-forming coupler. Such elements are, for example, described inHansen, U.S. Pat. No. 2,449,966. Suitable nondiffusing couplers aredescribed in U.S. Pat. Nos. 2,956,876, 2,407,293, and 2,640,776.

The method for processing exposed films of the type mentioned and forutilizing replenishers, especially developer replenishers, whereby theconcentration of desirable components in the various processingsolutions, especially in the developer, are controlled betweenpredetermined concentration limits involves:

a. applying to the exposed film an aqueous developer having a pH of fromabout 10.5-11, desirably between about 10.6 and l0.75 when measured at75 F., and containing the pphenylenediamine color-developing agent,benzyl alcohol, and sulfite to develop the exposed silver halide and toform dye images in the exposed areas;

b. adding developer replenisher as described above to said developerwhereby the concentration of desirable components of said developer ismaintained between predetermined concentration levels;

c. contacting the developed film with an acidic composition,

e.g., containing acetic acid, to stop development;

d. treating the film with a gelatin hardening composition, e.g.,containing formaldehyde and methanol;

e. treating the film with a bleach composition, e.g., containingferricyanide and bromide, to oxidize the AG" to AG and f. treating thefilm with a fixing composition, e.g., hypo, to remove silver salts fromthe developed film.

Desirably, washing steps follow each of the hardening,

' bleaching, and fixing steps and, prior to drying the processed film,it is usually recommended that the film is treated in a final rinsecomposition to prevent the formation of water spots" on the film. Thetimes and temperatures for each of the processing steps may be varied.However, it is usually desirable to maintain the temperature of thedeveloper relatively constant. Dwell times and bath temperatures whichare generally used for continuous machine processing in standardsolutions are as follows: Develop 12 minutes at 75 F. and stop 4minutes; harden 6 minutes; wash 4 minutes; bleach 6 minutes; wash 4minutes; fix 8 minutes; wash 8 minutes; and final rinse 1 minute, all at73-77 F. and drying at elevated temperature, e.g., -l 10 F.

The developer advantageously contains substantially the same ingredientsas the developer replenisher described above. The same developing agent,for example, is desirably used in both the developer and replenisher.Similarly, benzyl alcohol, sulfite, and buffer are desirably utilized inthe developer. However, according to the present invention theconcentrations of various ingredients in the developer vary considerablyfrom those of the replenisher. Although the potassium/sodium ratio inthe developer, for example, is desirably similar to that of thedeveloper replenisher, the ratio in the developer is not very important.The potassium/sodium ratio is extremely important in the replenishersand replenisher kits of the present invention.

To obtain optimum effectiveness it is very important that theconcentration of benzyl alcohol in the replenisher be at least 0.2 g.per liter greater than the concentration of benzyl alcohol in thedeveloper. in the developer, a benzyl alcohol concentration of 3.8 toabout 7.8 g. per liter is suitable. A concentration of benzyl alcohol inthe developer of about 5.6 to about 6.0 g. per liter is especiallyeffective while a concentration of about 6.2 to about 7.2 per literbenzyl alcohol would be suitable for a corresponding replenishersolution.

It is also important to optimum effectiveness that the developing agentbe present in a higher concentration in the replenisher than in thedeveloper by at least 0.4 g. per liter based on the weight of availablediamine especially when the replenisher contains about 3 g. to about 5g. developing agent selected from the group consisting of 2-amino-5-diethylamino-toluene; 4-amino-N-ethyl-N-[B-methanesulfonamidoethyll-m-toluidine; 4-amino-3-methyl-N-ethyl-N-[ B-hydroxyethyl]-aniline; and4-amino-3-[Bmethylsulfonamidoethyl]-N,N-diethylaniline. About 3.2 toabout 3.8 g. 4-amino-N-ethyl-N-[B-methanesulfonamidoethyl]-mtoluidineper liter is especially effective for the developer, while thecorresponding concentration for a replenisher used with such a developeris about 3.9 to about 4.5 g. 4-amino-N-ethyl-N-[B-methanesulfonamidoethyl]-m-toluidine per liter.

It is extremely important to maximum effectiveness of the system thatthe bromide concentration of the replenisher be substantially lower thanthe concentration of bromide in the developer. For example, thedeveloper bromide concentration is nearly always at least 1 g. per liter(corresponding to at least about 1.3 g. sodium bromide per liter)whereas for optimum effectiveness the replenisher bromide concentration,if any is present, should be no greater than about 0.80 g. per liter(corresponding to about 1 g. sodium bromide). In one advantageousembodiment of the present invention the bromide concentration is betweenabout 0.60 and 0.80 g. per liter.

Sulfite concentrations for the developer can vary somewhat but formaximum effectiveness should be between about 1.2 g. (e.g., supplied asabout 1.9 g. sodium sulfite) to about 1.5 g. per liter. Thecorresponding replenisher then would desirably contain slightly morethan the developer, about l.25 to about 1.55 g. per liter. As with thereplenisher, the sulfite is normally supplied to the solution as analkali metal sulfite or bisulfite.

The developer also desirably contains a buffer system which is providedin a manner analogous to that for the replenisher except that theresultant pH is desirably slightly lower for the developer. Highlysuitable buffer systems result from the dissolution of boric acid andalkali metal hydroxides so that the total borate concentration,including boric acid and/or dissociated residues thereof, is about 26.5to about 27.0 g. per liter. A replenisher for such a developer desirablywould have a total borate concentration of about 27.2 to about 27.8 g.per liter.

. The developer also desirably contains sequestering agent, desirablythe dissolved residues from about 0.8 to about 1.3 g. per liter ofdiaminopropanol tetraacetic acid. With such a developer, a replenisherhaving the same sequestering agent in a concentration of about 1.0 toabout 1.5 g. per liter would advantageously be utilized.

As mentioned above the rate of replenishment can be decreasedsubstantially by the use of the developer replenishers of the presentinvention. Accordingly, rates of less than 300 ml. per square foot ofprocessed film are easily accomplished. Since decreasing thereplenishment rate can result in processing which compares favorably,with substantial reduction in cost of chemicals and pollutionprevention, in a highly advantageous embodiment of the present inventionthe developer replenishment rate is less than about 162 ml. replenisherper square foot of processed film (corresponding to about 243 ml.replenisher per square foot of picture area processed). Thereplenishment rate can, of course, be decreased even further in whichcase the differences in concentration between developer ingredients andreplenisher ingredients is even greater.

The following examples are intended to illustrate our invention and/oradvantages thereof;

EXAMPLE 1 A three-component developer replenisher kit is preparedcontaining Parts A, B, and C as follows:

Part A about 6.3 ml. benzyl alcohol.

Part B A concentrated buffer solution which is prepared by dissolving3.4 g. NaOH and 22.8 g. KOH in about 63 g. water;

then, slowly adding about 29 g. boric acid; and adjusting the pH of theresultant solution to about 10.75 at 80 F. by the addition of smallamounts of potassium hydroxide (45 percent solution).

PartC A concentrated acidic solution containing developing agent whichis prepared by dissolving about 2 g. sodium sulfite in about 1 l g.water, and adding about 6.4 g. 4-amino-N-ethyl-N-[B-methanesulfonamidoethyl]-m-toluidine sesquisulfate monohydrate withstirring.

EXAMPLE 2 A photographic developer replenisher is prepared by: addingthe 6.2 g. benzyl alcohol (Part A, Example 1) with vigorous stirring toabout 800 ml. water; adding to the resultant solution with stirring thesolution from Part B (Example 1 after Part B is fully dissolved, addingPart C (Example l) with stirring and adding water to adjust the volumeto 1 liter at 80 F.

EXAMPLE 3 The solution from Example 2 is then utilized as a developerreplenisher in processing an imagewise exposed commercially availablesilver halide sensitized color negative film material havingrespectively superposed on and adhered to-a transparent support ared-sensitized gelatinous emulsion layer containing nondiffusing cyandye-forming coupler, a green-sensitized gelatinous emulsion layercontaining nondifi'using magenta dye-forming coupler, a yellow filterlayer, and a bluesensitized emulsion layer containing nondiffusingyellow dyeforming coupler. The developer which is replenished containsthe dissolved residues from approximately 5.8 g. benzyl alcohol, 28.1 g.boric acid, 5.4 g. 4-amino-N-ethyl-N-[B-methanesulfonamidoethyll-m-toluidine sesquisulfate monohydrate, 1.9 g.sodium sulfite, 3.2 g. sodium hydroxide,

20.5 g. of potassium hydroxide, and about 1.5 g. sodium bromide perliter of solution.

The process involves developing the film as described above for a periodof about 14 minutes at about i.05 F. (about 24 C.), and the followingsteps in the order indicated at 7512 F.: stopping the development bytreating the developed film in an acetic acid stop bath for about4.minutes; treating the film in a gelatin hardener solution containingformaldehyde and methanol for about 4 minutes; washing the film inrunning water for about 4 minutes; treating the film in a bleach bathcontaining ferricyanide and bromide for about 6 minutes; washing thefilm in running water for about-4 minutes; treating the film in a hypofix bath for about 8 minutes; washing the fixed film for about 8minutes; and then drying the film at about 90 F. 1

The developer replenisher functions effectively when added to thedeveloper at a rateof about 243 ml. per square foot of picture areaproduced (about 163 ml. per square foot of film processed).

EXAMPLE 4 The procedure according to Example 3 is followed except thatthe developer replenisher contains about 0.9 g.- sodium bromide.High-quality development is obtained.

EXAMPLE 5 The procedure according to Example 3 is followed except thatthe developer contains the dissolved residues from about 1.16 g.diaminopropanol tetraacetic acid and the replenisher contains thedissolved residues from about 1.3 g. of the same compound plus about 0.9g. sodium bromide. Consistent, high-quality development is obtained at areplenishment rate of about 242 ml. per square foot of picture areaprocessed.

EXAMPLE 6 A two-component developer replenisher is prepared containingParts A and B as follows:

Part A An acidic aqueous developing agent which is prepared by: addingabout 0.3 g. sodium sulfite (about .19 g. sulfite) to about 8 g.distilled water and stirring until the sodium sulfite is completelydissolved; then dissolving about 6.4 g. 4-amino-N- ethyl-N-[,B-methanesulfon amidoethyl ]-m-toluidine sesquisulfate monohydrate inthe sulfite solution; adding to the resultant acidic solution about 6.6g. benzyl alcohol with vigorous stirring to form cloudy slurry; and thengradually adding ethylene glycol to the slurry until a clear solutionforms, about 7.8 g. This solution exhibits excellent storage stability.

Part B A buffered aqueous alkali solution which is prepared by:dissolving about 3.4 g. of sodium hydroxide and about 23.3 g. ofpotassium hydroxide in about 42 g. water; gradually adding to thissolution about 29 g. boric acid, about 1.7 g. sodium sulfite, about 1.3g. diaminopropanol tetraacetic acid, and about 0.8 g. sodium bromide andadjusting the pH to about 10.75%.05 at F. by the addition of smallamounts of potassium hydroxide. The solution is stable for long periodsof time at varying temperatures.

EXAMPLE 7 A developer replenisher is prepared by slowly adding thesolution from Example 6A to about 800 ml. of water and stirring toassure complete dissolution; slowly adding the solution from Example 68with stirring; and adding sufficient water to bring the total volume toone liter.

. EXAMPLE 8 The procedure according to Example 3 is followed except thatthe solution from Example 7 is utilized in place of the replenisher fromExample 2. Satisfactory results are achieved with a developerreplenisher rate of about 243 ml. per square foot of picture areaprocessed.

EXAMPLE 9 The procedure according to Example 8 is followed except thatthe developer of Example 3 also contains the dissolved residues fromabout 1.2 g. of diaminopropanol tetraacetic acid. Excellent results areachieved with a developer replenisher rate of about 243 ml. per squarefoot of picture area processed (about 160 ml. per square foot of filmprocessed).

EXAMPLE 10 A developer replenisher is prepared containing the dissolvedresidues from about 7 g. benzyl alcohol, about 29 g. boric acid, about3.4 g. sodium hydroxide, about 23.5 g. potassium hydroxide, about 2.1 g.sodium sulfite, about 1.3 g. diaminopropanol tetraacetic acid, about 0.4g. sodium bromide, and about 7.9 g.4-amino-N-ethyl-N-[fi-methanesulfonamidoethyl]-m-toluidine sesquisulfatemonohydrate per liter of aqueous solution. The resultant solution has apH of about 10.78 at 80 F. and shows no signs of crystallization orprecipitation at temperatures ranging as low as 50 F.

EXAMPLE 11 The procedure according to Example 3 is followed except thatthe solution from Example 10 is utilized in place of the solution fromExample 2 and the developer which is replenished contains about 1.2 g.diaminopropanol tetraacetic acid and about mg. potassium iodide.Satisfactory results are achieved at a replenishment rate of about 121ml. per square foot of picture area processed (about 80 ml. per squarefoot of processed film).

EXAMPLE 12 The procedure according to Example 11 is followed except thata developer replenisher containing about 7.7 g. benzyl alcohol, about 8g. ethylene glycol, about 1.3 g. diaminopropanol tetraacetic acid, about29 g. boric acid, about 3.4 g. sodium hydroxide, about 23.5 g. potassiumhydroxide, about 2.2 g. sodium sulfite, no bromide, and about 9.4 g.4-amino-N-ethyl-N-[B-methanesulfonamidoethyl]-mtoluidine sesquisulfatemonohydrate per liter of solution is used in place of the replenisherfrom Example 10. Satisfactory results are achieved at a developerreplenishment rate of about 77 ml. per square foot of picture areaprocessed (about 52 ml. per square foot of processed film).

EXAMPLE 13 The procedure according to Example 11 is followed except thata replenisher solution is prepared from a two-component replenisher kitby procedures outlined in Example 7. Part A of the replenisher kit isidentical to Example 6, Part A. Part B of the replenisher contains thesame ingredients but about 1 l g. more water than Example 6, Part B. Thereplenisher functions extremely effectively at a replenishment rate ofabout 243 ml. per square foot of picture area processed.

EXAMPLE l4 (Comparative Example) A composition is prepared by combiningabout 0.25 moles g.) sodium hydroxide, about 0.25 moles (14 g.)potassium hydroxide, about 6.4 g.4-amino-N-ethyl-N-[B-methanesulfonamidoethyl]-m-toluidine sesquisulfatemonohydrate, about 2 g. sodium sulfite, about 6.6 g. benzyl alcohol,about 7.8 g. ethylene glycol, about 29 g. boric acid, about 1.3 g.diaminopropanol tetraacetic acid, and 0.8 g. sodium bromide andsufficient water to make one liter total volume. The compositionfunctions poorly and is impractical as a developer replenisher forprocessing color film products according to the procedure of Example 3.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:

1. An aqueous developer replenisher having a pH of about 10.5 to 1 l andcontaining alkali metal cations, p-phenylenediamine developing agent,benzyl alcohol, and sulfite, said alkali metal ions consistingessentially of alkali metal ions selected from the group consisting ofpotassium and sodium ions in a potassium/sodium weight ratio of at least2.5/1 to 10/ 1.

2. The invention according to claim 1 and wherein said replenishercontains about 4 to about 8 g. per liter benzyl alcohol.

3. The invention according to claim 1 and wherein said replenishercontains about 6 to about 7.5 g. benzyl alcohol per liter of solution.

4. The invention according to claim 1 and wherein said developing agentis selected from the group consisting of 2- amino-S-diethylaminotoluene;4-amino-N-ethyl-N-[B- methanesulfonamidoethylLm-toluidine;4-amino-3-methyl-N- ethyl-N-[B-hydroxyethyl]-aniline; and4-amino-3-[B-methylsulfon-amidoethyl]-N,N-diethylaniline.

5. The invention according to claim 1 and wherein said developing agentis selected from the group consisting of 2- amino-S-diethylaminotoluene;methane-sulfonamidoethylI-m-toluidine; 4-amino-3-methyl-N-ethyl-N[B-hydroxyethyl]-aniline; and 4-amino-3-[B-methylsulfonamidoethyl]-N,N-diethylaniline; and is present at aconcentration of about 3 g. to about 5 g. per liter based on the weightof the available diamine.

6. The invention according to claim 1 and wherein said replenishercontains about-4 to about 8 g. per liter benzyl alcohol and about 3 toabout 5 g. per liter p-phenylenediamine developing agent based on theweight of available diamine and wherein said developing agent isselected from the group consisting of 2-amino-S-diethylaminotoluene;4-amino-N-ethyl- N-[B-methanesulfonamidoethyll-m-toluidine; 4-amino-3-methyl-N-ethyl-N-[B-hydroxyethyl]-aniline; and 4-amino-3-[B-methylsulfonamidoethyl]-N,N-diethylaniline.

7. The invention according to claim 1 and wherein said replenishercontains 6 to 7.5 g. benzyl alcohol and about 3.8 to about 4.5 g.4-amino-N-ethyl-N-[B-methanesulfonamidoethyl]-m-toluidine per liter ofsolution.

8. The invention according to claim 1 and wherein said sulfite ispresent in the replenisher at a concentration of about 1.25 g. to about1.55 g. per liter of solution.

9. The invention according to claim 1 and wherein said replenishercontains a buffering system.

10. The invention according to claim 1 and wherein said replenishercontains a boric acid-borate buffer.

11. The invention according to claim 1 and wherein said replenishercontains a boric acid-borate buffer to maintain the solution pH betweenabout 10.5 and 11 which buffer is provided in the solution byincorporating therein alkali metal hydroxides selected from the groupconsisting of potassium and sodium hydroxides provided that thepotassium/sodium weight ratio is between about 2.5/1 and 10/1 and 18 to30 g. boric acid per liter of solution.

12. The invention according to claim 1 and wherein said replenishercontains from about 4 to about 8 g. per liter benzyl alcohol, developingagent selected from the group consisting of2-amino-5-diethylaminotoluene; 4-amino-N-ethyl-N-[B-methanesulfonamidoethyll-m-toluidine; 4-amino-3-methyl-N-ethyl-N-[B-hydroxyethyl]-ani1ine; and4-amino-3-[B-methylsulfonamidoethyl]-N,N-diethylaniline at aconcentration from about 3 to about 5 g. per liter based on the weightof available diamine, about 1.25 to about 1.55 g. per liter sulfite,about 19 to about 28.5 g. borate, and from about 0.5 to about 2 g.sequestering agent.

13. The invention according to claim 1 and wherein said replenishercontains up to 0.80 g. bromide per liter of solution.

14. The invention according to claim 1 and wherein said replenishercontains from about 0.60 to about 0.80 g. bromide per liter of solution.

15. A developer replenisher comprising an aqueous composition having apH of about 10.5 to about 1 1.0 and containmg:

a. alkali metal cations consisting essentially of potassium and sodiumions in a potassium/sodium weight ratio of between 25/1 and 10/1;

b. benzyl alcohol c. p-phenylenediamine developing agent;

e. buffering system; and

f. sequestering agent.

16. A developer replenisher in accordance with claim 15 and wherein saidbenzyl alcohol concentration is between about 4 to about 8 g. per literand said developing agent is selected from the group consisting of2-amino-5- position having a pH of from about 10.6 to about 10.9containing:

a. alkali metal cations consisting essentially of potassium and sodiumions in a potassium/sodium weight ratio of about 4 to /1;

b. benzyl alcohol in a concentration of about 6 g. to about 7.5 g. perliter;

0. dissolved residues resulting from incorporating into solution about 6to about 7 g. 4-amino-N-ethyl-N-[B- methanesulfonamidoethyl]-m-toluidine sesquisulfate monohydrate per liter of replenishersolution;

.sulfite in a concentration of about 1.25 g. to about 1.55 g.

per liter of solution;

. a boric acid-borate buffer system which is provided in the solution byutilizing therefor alkali metal hydroxide, the resulting alkali metalions of which consist essentially of potassium and sodium ions and format least a part of the alkali metal ions in part (a), and the dissolvedresidues from about 25 to about 30 g. boric acid per liter ofreplenisher;

. the dissolved residues from the incorporating into the solution about1 to about 1.5 g. diaminopropanol tetraacetic acid per liter ofsolution; and

g. bromide in concentration of from about 0.60 to about 0.80 g. perliter of solution.

2. The invention according to claim 1 and wherein said replenishercontains about 4 to about 8 g. per liter benzyl alcohol.
 3. Theinvention according to claim 1 and wherein said replenisher containsabout 6 to about 7.5 g. benzyl alcohol per liter of solution.
 4. Theinvention according to claim 1 and wherein said developing agent isselected from the group consisting of 2-amino-5-diethylaminotoluene;4-amino-N-ethyl-N-( Beta -methanesulfonamidoethyl)-m-toluidine;4-amino-3-methyl-N-ethyl-N-( Beta -hydroxyethyl)-aniline; and4-amino-3-( Beta -methylsulfon-amidoethyl)-N,N-diethylaniline.
 5. Theinvention according to claim 1 and wherein said developing agent isselected from the group consisting of 2-amino-5-diethylaminotoluene;4-amino-N-ethyl-N-( Beta -methane-sulfonamidoethyl)-m-toluidine;4-amino-3-methyl-N-ethyl-N( Beta -hydroxyethyl)-aniline; and 4-amino-3-(Beta -methylsulfonamidoethyl)-N,N-diethylaniline; and is present at aconcentration of about 3 g. to about 5 g. per liter based on the weightof the available diamine.
 6. The invention according to claim 1 andwherein said replenisher contains about 4 to about 8 g. per liter benzylalcohol and about 3 to about 5 g. per liter p-phenylenediaminedeveloping agent based on the weight of available diamine and whereinsaid developing agent is selected from the group consisting of2-amino-5-diethylaminotoluene; 4-amino-N-ethyl-N-( Beta-methanesulfonamidoethyl)-m-toluidine; 4-amino-3-methyl-N-ethyl-N-( Beta-hydroxyethyl)-aniline; and 4-amino-3-( Beta-methylsulfonamidoethyl)-N,N-diethylaniline.
 7. The invention accordingto claim 1 and wherein said replenisher contains 6 to 7.5 g. benzylalcohol and about 3.8 to about 4.5 g. 4-amino-N-ethyl-N-( Beta-methanesulfonamidoethyl)-m-toluidine per liter of solution.
 8. Theinvention according to claim 1 and wherein said sulfite is present inthe replenisher at a concentration of about 1.25 g. to about 1.55 g. perliter of solution.
 9. The invention according to claim 1 and whereinsaid replenisher contains a buffering system.
 10. The inventionaccording to claim 1 and wherein said replenisher contains a boricacid-borate buffer.
 11. The invention according to claim 1 and whereinsaid replenisher contains a boric acid-borate buffer to maintain thesolution pH between about 10.5 and 11 which buffer is provided in thesolution by incorporating therein alkali metal hydroxides selected fromthe group consisting of potassium and sodium hydroxides provided thatthe potassium/sodium weight ratio is between about 2.5/1 and 10/1 and 18to 30 g. boric acid per liter of solution.
 12. The invention accordingto claim 1 and wherein said replenisher contains from about 4 to about 8g. per liter benzyl alcohol, developing agent selected from the groupconsisting of 2-amino-5-diethylaminotoluene; 4-amino-N-ethyl-N-( Beta-methanesulfonamidoethyl)-m-toluidine; 4-amino-3-methyl-N-ethyl-N-( Beta-hydroxyethyl)-aniline; and 4-amino-3-( Beta-methylsulfonamidoethyl)-N,N-diethylaniline at a concentration fromabout 3 to about 5 g. per liter based on the weight of availablediamine, about 1.25 to about 1.55 g. per liter sulfite, about 19 toabout 28.5 g. borate, and from about 0.5 to about 2 g. sequesteringagent.
 13. The invention according to claim 1 and wherein saidreplenisher contains up to 0.80 g. bromide per liter of solution. 14.The invention according to claim 1 and wherein said replenisher containsfrom about 0.60 to about 0.80 g. bromide per liter of solution.
 15. Adeveloper replenisher comprising an aqueous composition having a pH ofabout 10.5 to about 11.0 and containing: a. alkali metal cationsconsisting essentially of potassium and sodium ions in apotassium/sodium weight ratio of between 2.5/1 and 10/1; b. benzylalcohol c. p-phenylenediamine developing agent; d. sulfite; e. bufferingsystem; and f. sequestering agent.
 16. A developer replenisher inaccordance with claim 15 and wherein said benzyl alcohol concentrationis between about 4 to about 8 g. per liter and said developing agent isselected from the group consisting of 2-amino-5-diethylaminotoluene;4-amino-N-ethyl-N-( Beta -methanesulfonamidoethyl)-m-toluidine;4-amino-3-methyl-N-( Beta -hydroxyethyl)-aniline; and 4-amino-3-( Beta-methylsulfonamidoethyl)-N,N-diethylaniline.
 17. The invention accordingto claim 15 and wherein said developer contains up to about 0.80 g.bromide per liter of solution.
 18. A developer replenisher comprising anaqueous composition having a pH of from about 10.6 to about 10.9containing: a. alkali metal cations consisting essentially of potassiumand sodium ions in a potassium/sodium weight ratio of about 4 to 10/1;b. benzyl alcohol in a concentration of about 6 g. to about 7.5 g. perliter; c. dissolved residues resulting from incorporating into solutionabout 6 to about 7 g. 4-amino-N-ethyl-N-( Beta-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate perliter of replenisher solution; d. sulfite in a concentration of about1.25 g. to about 1.55 g. per liter of solution; e. a boric acid-boratebuffer system which is provided in the solution by utilizing thereforalkali metal hydroxide, the resulting alkali metal ions of which consistessentially of potassium and sodium ions and form at least a part of thealkali metal ions in part (a), and the dissolved residues from about 25to about 30 g. boric acid per liter of replenisher; f. the dissolvedresidues from the incorporating into the solution about 1 to about 1.5g. diaminopropanol tetraacetic acid per liter of solution; and g.bromide in concentration of from about 0.60 to about 0.80 g. per literof solution.